Alkenes palladium salt catalyst

Hydroxycarbonylation and alkoxycarbonylation of alkenes catalyzed by metal catalyst have been studied for the synthesis of acids, esters, and related derivatives. Palladium systems in particular have been popular and their use in hydroxycarbonylation and alkoxycarbonylation reactions has been reviewed.625,626 The catalysts were mainly designed for the carbonylation of alkenes in the presence of alcohols in order to prepare carboxylic esters, but they also work well for synthesizing carboxylic acids or anhydrides.137 627 They have also been used as catalysts in many other carbonyl-based processes that are of interest to industry. The hydroxycarbonylation of butadiene, the dicarboxylation of alkenes, the carbonylation of alkenes, the carbonylation of benzyl- and aryl-halide compounds, and oxidative carbonylations have been reviewed.6 8 The Pd-catalyzed hydroxycarbonylation of alkenes has attracted considerable interest in recent years as a way of obtaining carboxylic acids. In general, in acidic media, palladium salts in the presence of mono- or bidentate phosphines afford a mixture of linear and branched acids (see Scheme 9). 

Trialkylamines are used as additives in the telomerization of butadiene and water in a two-phase system (103). The catalyst comprises a palladium salt and tppms or tppts. The amines may build cationic surfactants under catalytic conditions and be capable of micelle formation. The products include up to five telomerization products (alcohols, alkenes, and ethers), and thus the reaction is nonselective. 

The catalyst The amount of catalyst required in an aryl bromide or iodide alkene substitution varies widely with the reactants and the reaction conditions. Most examples reported have used 1-2 mol % of palladium salt relative to the aryl halide, but much lower amounts are sufficient in some instances. In an extreme case, where very reactive p-nitrobromobenzene was added to the very active alkene, ethyl acrylate and sodium acetate was the base in DMF solution at 130 C with a palladium acetate-tri-o-tolylphos-phine catalyst in 6 h the palladium turned over 134 000 times and ethyl p-nitrocinnamate was obtained in 67% yield.63... 

Palladium(II) salts apparently oxidize arylamines to arylpalladium salts since alkenes are arylated by reaction with only an aromatic amine and a palladium salt. However, yields are generally low.100 Much better yields are obtained if /-butyl nitrite is added and, of course, this forms the diazonium salt in situ. This not only saves a step but some diazonium salts which are too unstable to be isolated may be used as well. The reactions are carried out in the presence of acetic or chloroacetic acid with 5-10% bis(di-benzylideneacetone)palladium as catalyst (equation 41).101... 

V,(V-Dichloro-p-toluenesulfonamidc (TsNCL) has been found to be an efficient nitrogen source for the aziridination of unfunctionalized alkenes using palladium catalysts. Among the palladium salts, (AcO Pd was the most effective catalyst.81... 

Heteropolyoxametalates are often used in combination with palladium salts as catalysts in oxidation processes using dioxygen as the oxidant. Indeed, the oxidative coupling reaction of benzenes with alkenes was also successfully achieved by use of the Pd(OAc)2/molybdovanadophosphoric acid (HPMoV)/02 system [14a]. For example, reaction of benzene with ethyl acrylate using this catalytic system in acetic acid afforded ethyl cinnamate as a major product in satisfactory yield. Typically, the reaction is conducted in acetic acid at 90 °C under 1 bar of 02. After 6 h the TON is 15. This number was recently improved to 121 [14b]. 

To overcome the problems encountered in the homogeneous Wacker oxidation of higher alkenes several attempts have been undertaken to develop a gas-phase version of the process. The first heterogeneous catalysts were prepared by the deposition of palladium chloride and copper chloride on support materials, such as zeolite Y [2,3] or active carbon [4]. However, these catalysts all suffered from rapid deactivation. Other authors applied other redox components such as vanadium pentoxide [5,6] or p-benzoquinone [7]. The best results have been achieved with catalysts based on palladium salts deposited on a monolayer of vanadium oxide spread out over a high surface area support material, such as y-alumina [8]. Van der Heide showed that with catalysts consisting of H2PdCU deposited on a monolayer vanadium oxide supported on y-alumina, ethene as well as 1-butene and styrene... 

Palladium catalysts are best known for oxidizing alkenes to ketones or vinyl derivatives. However, formation of a,P-unsaturated carbonyl compounds by UV irradiation of oxygenated solutions of alkenes in the presence of catalytic amounts of palladium salts has been observed by Muzart. - This reaction is believed to proceed through a ir-allylpalladium trifluoroacetate complex, e.g. (77). 

Partial reduction of alkynes to Z-alkenes is another important application of selective hydrogenation catalysts. The transformation can be carried out under heterogeneous or homogeneous conditions. Among heterogeneous catalysts, the one which is most successful is Lindlars catalyst, which is a lead-modified palladium-CaC03 catalyst. A nickel-boride catalyst prepared by reduction of nickel salts with NaBILj is also useful. Rhodium catalysts have also been reported to show good selectivity. ... 

This approach has been used to efficiently assemble 3-vinyl indoles 13 with alkenes (Scheme 6.20) [28]. It was observed in this case that the nature of the nitrogen substituent influences the ability to trap the 3-palladated indole, with carbamates providing the highest yields. The elimination of HX from the palladium after P-hydride elimination creates a Pd(0) complex that is unable to mediate subsequent cyclizations. As such, co-oxidants, such as stoichiometric copper(II) salts, are used in this reaction to regenerate the palladium(II) catalyst. However, by modifying reaction conditions, Lu has found that the addition of excess LiBr can inhibit P-hydride elimination, and instead allow the formation of the reduced product (Scheme 6.21) [29]. This not only allows access to 3-alkyl substituted indoles, but also eliminates the need for stoichiometric oxidants. 

The combination of palladium(II) catalysts with stoichiometric amounts of cop-per(I I) salts as oxidants allowed the subsequent development of further diamination reactions. A particularly attractive approach to cychc guanidines 144 from easily accessible precursors 143 was realized within such a diamination reaction of alkenes (Scheme 16.38) [SK)]. It is interesting to note that the reaction proceeds already with copper(II) dichloride and with unprecedentedly enhanced rates also for piperidine formation. The selection of carbamate protecting groups readily provides the free guanidinium products within a single-step transformation. 

In [51], Wacker oxidation of olefins was studied in the presence of catalytic systems comprising water-soluble calixarenes (sulfonated and glycydylated derivatives), palladium salt, and copper salt. The presence of nonpolar cavities in these molecules enables binding nonpolar substrates and their transfer into the aqueous phase where the reaction takes place. The activity of these catalysts depends on the complementarity between the cavity size of the host molecule and the size of the guest molecule. Therefore, substrate selectivity was exhibited. For example, the addition of calixarene increased the reaction rate for linear 1-alkenes which size corresponded to the size of the calixarene cavity (1-hexene for calix[4]arene and 1-octene for calix[6]arene). The activity of catalytic system applied for the oxidation of substituted styrenes also depended on the ratio of the size of the substrate molecule and that of the calixarene cavity. 

Cycloisomerization of dienes is also possible. Catalysts that have been used include rhodium (Scheme 11.80), ° ruthenium and palladium salts (Scheme 11.81) in alcohol solvents. Palladium NHC complexes are also efficient catalysts.The most likely mechanism involves the formation of a metal hydride, which acts as the catalyst. In some cases, alkene migration may also be observed and, with the right choice of catalyst, may become the exclusive pathway, as in the formation of cyclopentene 11.242. ... 

In an extension of this work, the Shibasaki group developed the novel transformation 48—>51 shown in Scheme 10.25c To rationalize this interesting structural change, it was proposed that oxidative addition of the vinyl triflate moiety in 48 to an asymmetric palladium ) catalyst generated under the indicated conditions affords the 16-electron Pd+ complex 49. Since the weakly bound triflate ligand can easily dissociate from the metal center, a silver salt is not needed. Insertion of the coordinated alkene into the vinyl C-Pd bond then affords a transitory 7t-allylpalladium complex 50 which is captured in a regio- and stereocontrolled fashion by acetate ion to give the optically active bicyclic diene 51 in 80% ee (89% yield). This catalytic asymmetric synthesis by a Heck cyclization/ anion capture process is the first of its kind. 

The reaction of alcohols with CO was catalyzed by Pd compounds, iodides and/or bromides, and amides (or thioamides). Thus, MeOH was carbonylated in the presence of Pd acetate, NiCl2, tV-methylpyrrolidone, Mel, and Lil to give HOAc. AcOH is prepared by the reaction of MeOH with CO in the presence of a catalyst system comprising a Pd compound, an ionic Br or I compound other than HBr or HI, a sulfone or sulfoxide, and, in some cases, a Ni compound and a phosphine oxide or a phosphinic acid.60 Palladium(II) salts catalyze the carbonylation of methyl iodide in methanol to methyl acetate in the presence of an excess of iodide, even without amine or phosphine co-ligands platinum(II) salts are less effective.61 A novel Pd11 complex (13) is a highly efficient catalyst for the carbonylation of organic alcohols and alkenes to carboxylic acids/esters.62... 

A number of examples have been reported documenting the use of palladium phosphine complexes as catalysts. The dialkyl species [PtL2R2] (L2 = dmpe, dppe, (PMe3)2 R = Me, CH2SiMe3) catalyze the reaction of [PhNH3]+ with activated alkenes (acrylonitrile, methyl acrylate, acrolein).176 Unfunctionalized alkenes prove unreactive. The reaction mechanism is believed to proceed via protonation of Pt-R by the ammonium salt (generating PhNH2 in turn) and the subsequent release of alkane to afford a vacant coordination site on the metal. Coordination of alkene then allows access into route A of the mechanism shown in Scheme 34. Protonation is also... 

In order to keep the mild conditions, hydroxycarbonylation has been performed in biphasic media, maintaining the catalyst in the aqueous phase thanks to water-soluble mono- or diphosphine ligands. In the presence of the sodium salt of trisulfonated triphenylphosphine (TPPTS), palladium was shown to carbonylate efficiently acrylic ester [19], propene and light alkenes [20,21] in acidic media. For heavy alkenes the reduced activity due to the mass transfer problems between the aqueous and organic phases can be overcome by introducing an inverse phase transfer agent, and particularly dimeihyl-/-i-cyclodextrin [22,23]. Moreover, a dicationic palladium center coordinated by the bidentate diphosphine ligand 2,7-bis(sulfonato)xantphos (Fig. 2) catalyzes, in the presence of tolylsulfonic acid for stability reasons, the hydroxycarbonylation of ethylene, propene and styrene and provides a ca. 0.34 0.66 molar ratio for the two linear and branched acids [24],... 

The metal-catalysed autoxidation of alkenes to produce ketones (Wacker reaction) is promoted by the presence of quaternary ammonium salts [14]. For example, using copper(II) chloride and palladium(II) chloride in benzene in the presence of cetyltrimethylammonium bromide, 1-decene is converted into 2-decanone (73%), 1,7-octadiene into 2,7-octadione (77%) and vinylcyclohexane into cyclo-hexylethanone (22%). Benzyltriethylammonium chloride and tetra-n-butylammo-nium hydrogen sulphate are ineffective catalysts. It has been suggested that the process is not micellar, although the catalysts have the characteristics of those which produce micelles. The Wacker reaction is also catalysed by rhodium and ruthenium salts in the presence of a quaternary ammonium salt. Generally, however, the yields are lower than those obtained using the palladium catalyst and, frequently, several oxidation products are obtained from each reaction [15]. 

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